Treatment liquid composition, inkjet ink composition, combination of treatment liquid composition and treatment method

Abstract

The present invention provides a treatment liquid composition, an inkjet ink composition, a combination of the treatment liquid composition and a treatment method, which can obtain an image having excellent color development, excellent wet friction fastness and light resistance that is difficult to fade even when wet friction. The treatment liquid composition contains: a water-resistant agent selected from polyamide epihalohydrin polymers and dimethylpyrazole blocked isocyanate; and a polyamine compound.

Description

Technical Field

[0001] The present invention relates to a treatment liquid composition, a combination of an inkjet ink composition and a treatment liquid composition, and a treatment method. Background Art

[0002] The inkjet recording method is a method of recording by ejecting droplets of an inkjet ink composition (hereinafter also referred to as "ink") from a fine nozzle and attaching them to a recording medium. Conventionally, the following technology is known: when the ink is ejected onto a recording medium to form an image by the inkjet recording method, a treatment liquid composition containing a coagulant is used to pre-treat the recording medium in order to improve the color development of the recorded object.

[0003] For example, Patent Document 1 describes a treatment liquid composition containing a water-soluble cationic polymer obtained by reacting monomers including an amine and an epihalohydrin, a nonionic resin, an organic solvent, and water.

[0004] Patent Document 1: Japanese Patent Application Publication No. 2021-020394

[0005] However, it is difficult to achieve both excellent color development and excellent wet friction fastness that is difficult to fade even when wet rubbed. In addition, it is also difficult to make the cloth to which the treatment liquid composition is attached not easily yellowed and have excellent light resistance. Summary of the invention

[0006] One embodiment of the treatment liquid composition according to the present invention contains:

[0007] A water-resistance agent selected from polyamide epihalohydrin polymers and dimethylpyrazole blocked isocyanates; and

[0008] Polyamine compounds.

[0009] One embodiment of the set of the inkjet ink composition and the treatment liquid composition according to the present invention is:

[0010] The group is a group of an inkjet ink composition and the above-mentioned treatment liquid composition,

[0011] The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles. The ink composition has a pH of more than 8 and contains particle components having a volume average particle diameter of 20 nm to 500 nm.

[0012] One embodiment of the processing method according to the present invention comprises:

[0013] an attachment step of attaching the above-mentioned treatment liquid composition to the fabric; and

[0014] a heating step of heating the fabric to which the treatment liquid composition is attached,

[0015] The surface temperature of the fabric in the heating step is 100° C. or higher. DETAILED DESCRIPTION

[0016] Hereinafter, embodiments of the present invention will be described. The embodiments described below illustrate examples of the present invention. The present invention is not limited to the following embodiments, and also includes various modifications implemented within the scope of not changing the gist of the present invention. In addition, all the structures described below are not necessarily the necessary structures of the present invention.

[0017] 1. Treatment liquid composition

[0018] The treatment liquid composition of the present embodiment contains a water-resistance agent and a polyamine compound. The water-resistance agent is selected from a polyamide epihalohydrin polymer and a dimethylpyrazole blocked isocyanate.

[0019] 1.1.Hydration-resistant agent

[0020] The treatment liquid composition may contain one or both of a polyamide epihalohydrin polymer and a dimethylpyrazole blocked isocyanate as a water resistance agent. In addition, the treatment liquid composition may contain two or more polyamide epihalohydrin polymers or dimethylpyrazole blocked isocyanate as a water resistance agent.

[0021] 1.1.1. Polyamide epihalohydrin polymers

[0022] The polyamide epihalohydrin polymer refers to a polymer obtained by polymerizing a monomer containing an amine and an epihalohydrin. Examples of the polyamide epihalohydrin polymer include polyamine-epihalohydrin copolymers, polyamide-epihalohydrin copolymers, polyamide polyamine-epihalohydrin copolymers, and amine-epihalohydrin copolymers. These polymers can be obtained by the following well-known methods: a method of polymerizing a monomer containing an amine and an epihalohydrin, a method of grafting a monomer containing an epihalohydrin onto a polyamide obtained by polymerizing a monomer containing an amine and a carboxylic acid, and the like.

[0023] Epihalohydrin contains halogen atoms in its structure. As halogen atoms, for example, F, Cl, Br, I, etc. can be cited. Cl is preferred among these halogen atoms, so epihalohydrin is preferably epichlorohydrin. Therefore, as a polyamide epihalohydrin polymer, a polyamide epichlorohydrin polymer is preferred, specifically, preferably a polyamine-epichlorohydrin copolymer, a polyamide-epichlorohydrin copolymer, a polyamide polyamine-epichlorohydrin copolymer, an amine-epichlorohydrin copolymer. Among them, a polyamide-epichlorohydrin copolymer is more preferred.

[0024] Commercially available products of the polyamide epihalohydrin polymer include WS-4020, 4030, 4027, and TS-4070 (manufactured by Seikyo PMC Co., Ltd., polyamide-epichlorohydrin polymer), WS-4011 (manufactured by Seikyo PMC Co., Ltd., polyamine-epichlorohydrin polymer), AF-100, 251S, 255, 255LOX, and 2500 (manufactured by Arakawa Chemical Industries, Ltd., polyamide polyamine-epichlorohydrin polymer), Catiomaster PE-30 (manufactured by Yokkaichi Kosei Co., Ltd., dimethylamine-ethylenediamine-epichlorohydrin condensate), and EPA-SK01 (manufactured by Yokkaichi Kosei Co., Ltd., polyamide polyamine-epichlorohydrin condensate).

[0025] The polyamide epihalohydrin polymer may be used alone or in combination of two or more.

[0026] The weight average molecular weight of the polyamide epihalohydrin polymer is preferably 10,000 to 5,000,000, more preferably 100,000 to 5,000,000, further preferably 500,000 to 5,000,000, and particularly preferably 1,000,000 to 5,000,000. When the weight average molecular weight of the polyamide epihalohydrin polymer is within the above range, the wet friction fastness of an image formed by using the polyamide epihalohydrin polymer together with the inkjet ink composition is improved.

[0027] The content of the polyamide epihalohydrin polymer is preferably 0.10% by mass or more, more preferably 0.30% by mass or more, further preferably 0.50% by mass or more, and particularly preferably 0.70% by mass or more, relative to the total mass of the treatment liquid composition. In addition, the content of the polyamide epihalohydrin polymer is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, further preferably 1.5% by mass or less, and particularly preferably 1.2% by mass or less, relative to the total mass of the treatment liquid composition. When the content of the polyamide epihalohydrin polymer is within the above range, a record having a better balance of color development, dry friction fastness, wet friction fastness, texture, and light fastness can be formed.

[0028] 1.1.2. Dimethylpyrazole blocked isocyanate

[0029] Dimethylpyrazole blocked isocyanate is a compound in which the isocyanate group of an isocyanate compound is blocked with a dimethylpyrazole group. That is, a compound in which the isocyanate group is stabilized by masking the isocyanate group with dimethylpyrazole (preferably 3,5-dimethylpyrazole) as a blocking agent. As a result, the handling is safe, and the blocking agent is dissociated by heating and other treatments, and the isocyanate group is regenerated, thereby showing high reactivity. By using dimethylpyrazole blocked isocyanate, yellowing of the fabric is suppressed, and light resistance can be improved.

[0030] As the isocyanate compound, there is no particular limitation as long as there are at least two isocyanate groups in the molecule, and well-known polyisocyanate compounds can be used. For example, diisocyanate compounds such as alkylene (preferably having 1 to 12 carbon atoms) diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers and trimers of these diisocyanate compounds can be cited.

[0031] In addition, as a modified polyisocyanate compound derived from a diisocyanate compound, there is no particular limitation as long as it has two or more isocyanate groups, and examples thereof include polyisocyanates having a biuret structure, an isocyanurate structure, an urethane structure, a uretdione structure, an allophanate structure, a trimer structure, and an adduct of an aliphatic isocyanate of trimethylolpropane, etc. In addition, polymeric MDI (MDI=diphenylmethane diisocyanate) can also be used as a polyisocyanate compound.

[0032] Commercially available dimethylpyrazole blocked isocyanates can be used. Examples of commercially available dimethylpyrazole blocked isocyanates include "NK-assisted" series such as NK-assisted FU, NK-assisted IS-100, NK-assisted IS-80, NK-assisted V, NK-assisted NY, NK-assisted NY-27, NK-assisted NY-30, and NK-assisted NY-50 manufactured by Nichika Chemical Co., Ltd., and Fixer series manufactured by Murayama Chemical Research Institute Co., Ltd.

[0033] The isocyanate group generated by dimethylpyrazole blocked isocyanate can react with a substance having a hydroxyl group such as cellulose. In addition, the isocyanate group can also react with groups other than hydroxyl groups, and these reactions can be controlled by temperature and concentration.

[0034] When the fabric to which the treatment liquid composition is attached contains cellulose, the isocyanate group generated by the dimethylpyrazole blocked isocyanate reacts with the hydroxyl group of the cellulose to generate a urethane bond, and the two can be chemically bonded. In addition, by adjusting the degree and concentration of heating, the degree of reaction with cellulose and the like can be controlled, for example, after the treatment liquid composition is attached to the fabric, part or all of the blocked isocyanate groups can remain on the fabric without reacting.

[0035] In addition, a urethane bond is generated by the reaction of an isocyanate group with a hydroxyl group. However, the object that reacts with an isocyanate group is not limited to a hydroxyl group, and the other party of the reaction can also be changed according to the various chemical structures contained in the object. For example, a urea bond (urea bond) is generated when an isocyanate group reacts with an amino group, a urea bond is generated by the reaction of multiple isocyanate bonds with water, a biuret bond is generated by the reaction of a urea bond with an isocyanate group, and an allophanate bond is generated by the reaction of a urethane bond with an isocyanate group. These bonds can be actively generated or not generated by the reaction temperature, etc., and therefore, bonds can also be generated according to the chemical structure present in the object to which the treatment liquid composition is attached.

[0036] The content of the dimethylpyrazole blocked isocyanate is 0.1% by mass or more and 15.0% by mass or less, preferably 0.2% by mass or more and 10.0% by mass or less, more preferably 0.2% by mass or more and 5.0% by mass or less, and further preferably 0.5% by mass or more and 2.0% by mass or less, relative to the total amount of the treatment liquid composition. When the content of the dimethylpyrazole blocked isocyanate is within the above range, it is easy to bind and / or configure an appropriate amount of isocyanate groups to the fabric to which it is attached. For example, when the inkjet ink composition is attached to the fabric and heated, the components of the inkjet ink composition can react with the isocyanate groups. As a result, for example, the color material contained in the inkjet ink composition can be made difficult to fall off from the fabric, and the wet friction fastness of the image can be fully obtained.

[0037] 1.2. Polyamine compounds

[0038] The treatment liquid composition contains a polyamine compound. The polyamine compound has the properties of a cationic polymer. As the polyamine compound, any compound having an amino group in the structure can be used, and well-known polyamine compounds can be appropriately selected for use. For example, polyamine resins, polyamide resins, polyallylamine resins, etc. can be listed. Polyamine resins are resins having amino groups in the main skeleton of the resin. Polyamide resins are resins having amide groups in the main skeleton of the resin. Polyallylamine resins are resins having a structure derived from allyl groups in the main skeleton of the resin.

[0039] Commercially available products of polyamine compounds include: Unisense KHE103L manufactured by Senka Co., Ltd. (hexamethylenediamine / epichlorohydrin resin, a 1% aqueous solution has a pH of about 5.0, a viscosity of 20 to 50 (mPa·s), and an aqueous solution with a solid content concentration of 50% by mass), and Unisense KHE 104L (dimethylamine / epichlorohydrin resin, a 1% aqueous solution has a pH of about 7.0, a viscosity of 1 to 10 (mPa·s), and an aqueous solution with a solid content concentration of 20% by mass). Specific examples of commercially available cationic polyamine resins include FL-14 (manufactured by SNF), Arafix 100, 251S, 255, 255LOX (manufactured by Arakawa Chemical Co., Ltd.), DK-6810, 6853, 6885; WS-4010, 4011, 4020, 4024, 4027, 4030 (manufactured by Starlight PMC Co., Ltd.), Papyogen P-105 (manufactured by Senka Co., Ltd.), ), SumirezResin650(30), 675A, 6615, SLX-1 (manufactured by Taoka Chemical Industry Co., Ltd.), CatioMaster (registered trademark) PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (manufactured by Yokkaichi Synthetic Co., Ltd.), JetFix36N, 38A, N700, 5052 (manufactured by Satoda Chemical Co., Ltd.).

[0040] Examples of the polyallylamine resin include polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride-diallylamine hydrochloride copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine hydrochloride-dimethylallylamine hydrochloride copolymer, allylamine-dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate-sulfur dioxide copolymer, diallylmethylethylammonium ethylsulfate-sulfur dioxide copolymer, methyldiallylamine hydrochloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, and diallyldimethylammonium chloride-acrylamide copolymer.

[0041] The polyamine compound has the function of aggregating the components of the inkjet ink composition. Such aggregating can, for example, improve the color development of the pigment and / or improve the fixing property of the resin particles.

[0042] The content of the polyamine compound is 0.1% by mass or more and 15.0% by mass or less, preferably 0.2% by mass or more and 10.0% by mass or less, more preferably 0.2% by mass or more and 5.0% by mass or less, and further preferably 0.5% by mass or more and 2.0% by mass or less, relative to the total amount of the treatment liquid composition. When the content of the polyamine compound is within the above range, the dispersed components in the inkjet ink composition can be well agglomerated. Thus, for example, the color development of the color material contained in the inkjet ink composition can be fully obtained.

[0043] 1.3. Other ingredients

[0044] 1.3.1. Solvent

[0045] water

[0046] The treatment liquid composition involved in this embodiment preferably contains water as a solvent. Water can be the main solvent of the treatment liquid composition, and is a component that evaporates and disperses by drying. As water, for example, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and water such as ultrapure water from which ionic impurities are removed as much as possible can be cited. In addition, when water that has been sterilized by irradiation with ultraviolet rays or addition of hydrogen peroxide is used, it is possible to prevent the generation of mold and bacteria when the treatment liquid composition is stored for a long time.

[0047] The water content is not particularly limited, and can be, for example, 50% by mass or more, 60% by mass or more, or 70% by mass or more relative to the total mass of the treatment liquid composition. In addition, the upper limit of the water content in the treatment liquid composition can be 99% by mass or less, 98% by mass or less, or 97% by mass or less.

[0048] Water-soluble organic solvents

[0049] The treatment liquid composition according to the present embodiment may contain a water-soluble organic solvent as a solvent.

[0050] Examples of the water-soluble organic solvent include polyol compounds, glycol ethers, and betaine compounds.

[0051] Examples of the polyol compound include polyol compounds (preferably diol compounds) having 2 to 6 carbon atoms in the molecule and optionally having one ether bond in the molecule. Specific examples include 1,2-pentanediol, methyl triglycol (triethylene glycol monomethyl ether), butyl triglycol (triethylene glycol monobutyl ether), trimethylolpropane, butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether, glycerol, 1,2-hexanediol, 1,2-heptanediol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2- Methyl-3-phenoxy-1,2-propanediol, 3-(3-methylphenoxy)-1,2-propanediol, 3-hexyloxy-1,2-propanediol, 2-hydroxymethyl-1,2-phenoxymethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, and the like.

[0052] As glycol ethers, for example, monoalkyl ethers of glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol are preferred. More preferably, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, and dipropylene glycol monopropyl ether are listed.

[0053] Betaine compounds refer to compounds (intramolecular salts) having positive and negative charges at non-adjacent positions in the same molecule, dissociable hydrogen atoms not bound to atoms having positive charges, and having no charge as a whole molecule. Preferred betaine compounds are N-alkyl substituted amino acids, and more preferably N-trialkyl substituted amino acids. Examples of betaine compounds include trimethylglycine (also called "glycine betaine"), γ-butyl betaine, homarine, trigonelline, carnitine, homoserine betaine, valine betaine, lysine betaine, ornithine betaine, alanine betaine, stachydrine, and glutamic acid betaine, and preferably, trimethylglycine can be exemplified.

[0054] In addition, as the water-soluble organic solvent, a pyrrolidone derivative may be used, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, 5-methyl-2-pyrrolidone, etc.

[0055] The water-soluble organic solvent can be mixed and used in multiple forms. In addition, when the water-soluble organic solvent is contained, the content of the water-soluble organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less relative to the total mass of the treatment liquid composition.

[0056] 1.3.2. Surfactants

[0057] The treatment liquid composition according to the present embodiment may contain a surfactant. The surfactant has functions such as reducing the surface tension of the treatment liquid composition and improving wettability with a recording medium.

[0058] Among the surfactants, for example, acetylene glycol-based surfactants, silicone-based surfactants, and fluorine-based surfactants can be preferably used. Among them, acetylene glycol-based surfactants are more preferably contained.

[0059] The acetylene glycol surfactant is not particularly limited, and examples thereof include Surfynol 104 (HLB value = 4), 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485 (HLB value = 17), SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (all of the above are trade names, manufactured by Air Products and Chemicals, Inc.); Olfine B, Y, P, A, STG, SPC, E1004, E1010 (HLB value = 14), PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all of the above are trade names, manufactured by Nissin Chemical Industry Co., Ltd.); Acetylenol E00, E00P, E40, E100 (all of the above are trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0060] The silicone surfactant is not particularly limited, but preferably a polysiloxane compound is used. The polysiloxane compound is not particularly limited, and examples thereof include polyether-modified organosiloxanes. Commercially available products of the polyether-modified organosiloxane include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (these are trade names, manufactured by BYK Chemical Japan Co., Ltd.); KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (these are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.);

[0061] As the fluorine-based surfactant, a fluorine-modified polymer is preferably used, and a specific example thereof is BYK-340 (manufactured by BYK-Chemie Japan Ltd.).

[0062] The surfactant may be used alone or in combination of two or more.

[0063] The lower limit of the content of the surfactant is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more, relative to the total mass (100% by mass) of the treatment liquid composition. In addition, the upper limit of the content of the surfactant is preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, particularly preferably 2% by mass or less, and most preferably 1% by mass or less, relative to the total mass (100% by mass) of the treatment liquid composition.

[0064] When selecting a surfactant, the HLB value is preferably considered. The lower limit of the HLB value of the surfactant is preferably 6 or more, more preferably 8 or more, and further preferably 10 or more. In addition, the upper limit of the HLB value is preferably 18 or less, more preferably 16 or less, and further preferably 14 or less. When the HLB value is within the above range, the color rendering property may be further improved.

[0065] The HLB value in this specification refers to a value calculated from the ratio of the nonpolar value (I) to the polar value (O) in the organic concept diagram (hereinafter also referred to as "I / O value") by the following formula (1).

[0066] HLB value = (non-polar value (I) / polar value (O)) × 10…(1)

[0067] Specifically, the I / O value can be calculated based on the literature such as Fujita Mu's "Systematic Qualitative Analysis of Organic Mixtures", Kazama Shobo, 1974; Kuroki Nobuhiko's "Theoretical Chemistry of Dyeing", Maki Shoten, 1966; Inoue Hiroo's "Separation Methods of Organic Compounds", Soukabo, 1990.

[0068] 1.3.3. Water-insoluble components

[0069] The treatment liquid composition according to the present embodiment may contain a water-insoluble component. The water-insoluble component refers to a component that is insoluble or almost insoluble in water, and examples thereof include a water-insoluble colorant, a water-insoluble resin, wax, and a water-insoluble organic solvent.

[0070] Water-insoluble pigments

[0071] As water-insoluble color materials, oil-soluble dyes, pigment particles, etc. can be cited. As oil-soluble dyes, there are no particular limitations, and for example, disperse dyes, vat dyes, or organic solvent-soluble dyes can be used. As pigment particles, the same particles as those contained in the inkjet ink composition described later can be used.

[0072] Water-insoluble resin

[0073] Examples of water-insoluble resins include resins composed of, for example, urethane resins, acrylic resins, styrene acrylic resins, fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate resins. The water-insoluble resin is preferably used in the form of resin particles such as a resin emulsion or powder, and more preferably in the form of resin particles of a resin emulsion. The water-insoluble resin may be used alone or in combination of two or more.

[0074] Urethane resin is a general term for resins having urethane bonds. Urethane resins include polyether urethane resins having ether bonds in the main chain in addition to urethane bonds, polyester urethane resins having ester bonds in the main chain in addition to urethane bonds, and polycarbonate urethane resins having carbonate bonds in the main chain in addition to urethane bonds.

[0075] Acrylic resin is a general term for polymers obtained by polymerizing at least an acrylic monomer such as (meth)acrylic acid or (meth)acrylate as one component, and examples thereof include resins obtained from acrylic monomers, copolymers of acrylic monomers and other monomers, etc. Examples thereof include acrylic-vinyl resins which are copolymers of acrylic monomers and vinyl monomers, etc. Further examples thereof include copolymers with vinyl monomers such as styrene.

[0076] As acrylic monomers, acrylamide, acrylonitrile, etc. can also be used. As acrylic resins, commercial products can be used. In addition, in this specification, acrylic resins can also be styrene acrylic resins described later. In addition, in this specification, the expression of (meth) propylene means at least one of propylene and methpropylene.

[0077] Styrene acrylic resins are copolymers obtained from styrene monomers and acrylic monomers, and examples thereof include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, styrene-α-methylstyrene-acrylic acid-acrylate copolymers, etc. Commercially available styrene-acrylic resins can be used.

[0078] The polyolefin resin is a resin having an olefin such as ethylene, propylene, or butene in its structural skeleton, and a known polyolefin resin can be appropriately selected and used. As the olefin resin, a commercially available product can be used.

[0079] Examples of commercially available resin particle emulsions that can be used in the present embodiment are described below.

[0080] Urethane resin emulsion

[0081] Superflex 870, 800, 150, 420, 460, 470, 610, 620, 700, 460s, 840, E-4000 (trade name of Daiichi Kogyo Seiyaku Co., Ltd.), Permarin UA-150 (trade name of Sanyo Chemical Industries, Ltd.), Sancure 2710 (trade name of Nippon Lubrizol Co., Ltd.), NeoRez R-9660, R-9637, R-940 (trade name of Kusumoto Chemicals Co., Ltd.), Adeka Bon-Tighter HUX-380, 290K (trade name of ADEKA Co., Ltd.), Resamine D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade names manufactured by Dainichi Seika Industries, Ltd.), Takelac W-6020, W-635, W-6061, W-605, W-635, W-6021, W-512-A-6 (trade names manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.).

[0082] Acrylic resin emulsion

[0083] Voncoat 4001 (a trade name manufactured by DIC Corporation), Polysol AM-710, AM-920, AM-2300, AP-4735, AT-860, PSASE-4210E (a trade name manufactured by Showa Denko K.K.), Saivinol SK-200 (a trade name manufactured by Saiden Chemical Co., Ltd.), AE-120A (a trade name manufactured by JSR Corporation), Vinyblan 2682 (a trade name manufactured by Nissin Chemical Industry Co., Ltd.), Movinyl 952B, 718A (a trade name manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), K-854 (a trade name manufactured by Chuo Rika Industry Co., Ltd.), Nipol LX852, LX874 (a trade name manufactured by Nippon Zeon Co., Ltd.).

[0084] Styrene acrylic resin emulsion

[0085] MicroGel E-1002, E-5002 (trade name of Nippon Paint Co., Ltd.), Voncoat 5454 (trade name of DIC Corporation), Polysol AP-7020, SAE 1014 (trade name of Showa Denko Co., Ltd.), Vinyblan 2586 (trade name of Nissin Chemical Industry Co., Ltd.), Arrow Base CB-1200, CD-1200 (trade names manufactured by Unitika Co., Ltd.), Movinyl 966A, 7320, 975N (trade names manufactured by Nippon Synthetic Chemical Co., Ltd.), Joncryl 62J, 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (trade names manufactured by BASF).

[0086] Other resin emulsion

[0087] Elitel KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, KT-0507 (Unitika's trade name, polyester resin emulsion); Hytec SN-2002 (Toho Chemical's trade name, polyester resin emulsion); Polysol SH-502 (Showa Denko's trade name, vinyl acetate resin emulsion); Polysol AD-13, AD-2, AD-10, AD-96, AD-17, AD-70 (Showa Denko's trade name, ethylene-vinyl acetate resin emulsion); Polysol PSASE-6010 (Showa Denko's trade name, ethylene-vinyl acetate resin emulsion); AE373D (ETEC's trade name, carboxyl-modified styrene-acrylic resin emulsion); Seikadyne 1900W (a trade name manufactured by Dainichi Seika Industries, ethylene-vinyl acetate resin emulsion); Vinyblan 2886 (a trade name manufactured by Nissin Chemical Industries, Ltd., vinyl acetate-acrylic resin emulsion); Vinyblan 5202 (a trade name manufactured by Nissin Chemical Industries, Ltd., acetic acid acrylic resin emulsion); NK Binder R-5HN (a trade name manufactured by Shin-Nakamura Chemical Industries, Ltd.); Hydran WLS-210 (a trade name manufactured by DIC Corporation, non-cross-linked polyurethane emulsion).

[0088] wax

[0089] The wax is not particularly limited, and examples thereof include hydrocarbon waxes and ester waxes which are condensates of fatty acids and monohydric alcohols or polyhydric alcohols. The hydrocarbon wax is not particularly limited, and examples thereof include paraffin waxes and polyolefin waxes such as polyethylene wax and polypropylene wax. These waxes may be used alone or in combination of two or more.

[0090] Examples of commercially available paraffin waxes include AQUACER 497 and AQUACER 539 (these are product names, manufactured by BYK).

[0091] Examples of commercially available polyolefin waxes include Chemipearl S120, S650, and S75N (product names, manufactured by Mitsui Chemicals, Inc.), AQUACER 501, AQUACER 506, AQUACER 513, AQUACER 515, AQUACER 526, AQUACER 593, and AQUACER 582 (product names, manufactured by BYK).

[0092] The water-insoluble components may be used alone or in combination of two or more.

[0093] The treatment liquid composition involved in the present embodiment preferably does not contain water-insoluble components in a manner exceeding 1.0 mass % relative to the total mass of the treatment liquid composition, more preferably does not contain water-insoluble components in a manner exceeding 0.70 mass %, further preferably does not contain water-insoluble components in a manner exceeding 0.50 mass %, particularly preferably does not contain water-insoluble components in a manner exceeding 0.30 mass %, and more particularly preferably does not contain water-insoluble components in a manner exceeding 0.10 mass %, and may not contain water-insoluble components. Although there is a tendency to improve friction firmness, etc. by containing water-insoluble components, sometimes the coating stability is poor. In contrast, the treatment liquid composition involved in the present embodiment has the following tendency: even if the content of water-insoluble components is within the above range, the friction firmness is good, and the coating stability can be good. In addition, from the viewpoint of being able to further enjoy the effect of the present invention, the water-insoluble component is preferably a resin particle.

[0094] 1.4. Other ingredients

[0095] The treatment liquid composition according to the present embodiment may contain a pH adjuster, an antiseptic / antifungal agent, a rust preventive, a chelating agent, a viscosity adjuster, a solubilizing agent, an antioxidant, and the like, as necessary.

[0096] pH Adjusters

[0097] Examples of pH adjusters include: amines such as diethanolamine, triethanolamine, propanolamine, morpholine, and their modified products; organic acids such as acetic acid, citric acid, phthalic acid, oxalic acid, succinic acid, adipic acid, and amino acids; inorganic bases such as sodium hydroxide and potassium hydroxide; ammonium hydroxide, quaternary ammonium hydroxide (tetramethylammonium), and the like.

[0098] Preservatives / antifungal agents

[0099] Examples of the preservative and antifungal agent include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzisothiazolin-3-one (Proxel CRL, Proxel BND, Proxel GXL, Proxel XL-2, and Proxel TN manufactured by ICI).

[0100] Chelating agents

[0101] The chelating agent has the property of capturing ions. Examples of such chelating agents include ethylenediaminetetraacetate (EDTA), ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, and metaphosphate.

[0102] 1.5. Manufacturing method

[0103] The treatment liquid composition involved in this embodiment is obtained by mixing the above-mentioned components in any order and filtering to remove impurities as needed. As a mixing method for each component, it is preferred to use a method in which materials are added sequentially to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed. As a filtering method, centrifugal filtration, filter filtration, etc. can be performed as needed.

[0104] 1.6. Physical properties of treatment liquid composition

[0105] As the physical properties of the treatment liquid composition according to the present embodiment, pH, surface tension, viscosity, etc. can be adjusted to a desired range.

[0106] The treatment liquid composition involved in this embodiment preferably has a pH of less than 7. More preferably, the pH is less than 6, further preferably, the pH is less than 5, and particularly preferably, the pH is less than 4. The inkjet ink composition described later that can be used together with the treatment liquid composition involved in this embodiment often has a pH of more than 8 and is dispersed and stabilized. When the pH of the treatment liquid composition is within the above range, the ink tends to become dispersed and unstable when mixed with the inkjet ink composition, aggregation is promoted, and the reactivity with the ink becomes good, so that the color development property is sometimes further improved.

[0107] The surface tension of the treatment liquid composition according to the present embodiment at 25° C. is preferably 10 mN / m or more and 40 mN / m or less, and more preferably 25 mN / m or more and 40 mN / m or less. The surface tension can be measured by using, for example, an automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) and confirming the surface tension when the platinum plate is wetted with the treatment liquid composition in an environment of 25° C.

[0108] The viscosity of the treatment liquid composition involved in this embodiment at 20°C is preferably 2 mPa·s or more and 15 mPa·s or less, more preferably 2 mPa·s or more and 5 mPa·s or less, and further preferably 2 mPa·s or more and 3.6 mPa·s or less. The viscosity can be measured using, for example, a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica) to measure the viscosity in an environment of 40°C or 20°C.

[0109] 1.7. Purpose

[0110] The treatment liquid composition according to the present embodiment is preferably used for a water-based pigment inkjet ink. In addition, as the water-based pigment inkjet ink, the inkjet ink composition described below can be preferably used.

[0111] In addition, the treatment liquid composition involved in this embodiment is preferably applied to cloth for use. When forming an image on cloth with ink, high quality is required in terms of color development, wet friction fastness, texture, etc. According to the treatment liquid composition involved in this embodiment, there is a tendency that the excellent color development and excellent wet friction fastness required for forming an image on cloth can be taken into account, and the texture can also be good.

[0112] Materials constituting the cloth include, for example, natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable fibers such as polylactic acid. Blended fibers of these fibers are also possible.

[0113] In addition, the polyamide epihalohydrin polymer contained in the treatment liquid composition according to the present embodiment has the following functions: the amide part in the structure of the polyamide epihalohydrin polymer is combined with the hydroxyl group of the fiber of the fabric to reduce the swelling caused by the fiber containing water to improve the water resistance, and the function of improving the structural strength by cross-linking the epihalohydrin part, etc., at least one of which is exerted regardless of the raw material constituting the fabric. Therefore, regardless of whether the raw material constituting the fabric is natural fiber such as cotton or synthetic fiber such as polyester, the treatment liquid composition according to the present embodiment has an excellent effect of improving wet friction fastness.

[0114] Furthermore, since the dimethylpyrazole blocked isocyanate contained in the treatment liquid composition according to the present embodiment easily bonds to a hydroxyl group, the raw material constituting the fabric is more preferably a fiber containing cellulose such as cotton, whereby the image obtained exhibits excellent wet friction fastness.

[0115] The whiteness of the fabric is preferably 70 or more, more preferably 80 or more, and further preferably 90 or more. Whiteness is the L* value in the CIE / L*a*b* colorimetric system. Whiteness can be measured using a colorimeter "Gretag Macbeth Spectrolino" (product name, manufactured by X-Rite). Fabrics with a whiteness within the above range are relatively white fabrics, and therefore have a problem of yellowing that is particularly easy to be noticeable. However, since the treatment liquid composition involved in this embodiment is difficult to yellow, even such fabrics can be used without causing the problem of yellowing.

[0116] 1.8. Effects, etc.

[0117] The treatment liquid composition of the present embodiment can impart water resistance to the fiber of the recording medium through the water-resisting agent, easily suppress the swelling of the fiber, and make it difficult for the inkjet ink composition to be peeled off from the fiber. In addition, the treatment liquid composition of the present embodiment is easy to stay on the surface of the fiber of the recording medium and is difficult to dissolve by using the polyamine compound as a coagulant, so it can further react with the inkjet ink composition on the fiber surface. As a result, it is easy to maintain wet fastness and make the color development good. Moreover, the treatment liquid composition of the present embodiment can improve the light resistance of the image formed by the inkjet ink composition.

[0118] 2. Combination of inkjet ink composition and treatment liquid composition

[0119] An embodiment of the present invention relates to a combination of an inkjet ink composition and a treatment liquid composition, wherein the inkjet ink composition is an aqueous pigment inkjet ink comprising pigment particles and resin particles, wherein the pH of the ink composition exceeds 8 and comprises particle components having a volume average particle size of not less than 20 nm and not more than 500 nm.

[0120] In addition, the set of inkjet ink composition and treatment liquid composition may be any combination as long as the ink composition and treatment liquid composition included in the set are used for recording as a set. In other words, the ink composition and treatment liquid composition used for recording as a set are referred to as the set of inkjet ink composition and treatment liquid composition.

[0121] The set of the inkjet ink composition and the treatment liquid composition (hereinafter, also referred to as the "ink treatment liquid set") according to the present embodiment has an inkjet ink composition having a pH value of more than 8 and having a stable dispersion. When such an inkjet ink composition is mixed with the above-mentioned treatment liquid composition, the ink is easily converted into an unstable dispersion state and the aggregation of the particle components is promoted, so that the reactivity of the ink and the treatment liquid becomes good, and the color development property tends to be particularly excellent. Therefore, according to the ink treatment liquid set according to the present embodiment, it is possible to achieve both particularly excellent color development and excellent wet friction fastness.

[0122] Since the components of the treatment liquid composition included in the ink treatment liquid set according to the present embodiment are as described above, the description thereof will be omitted. Hereinafter, the components contained in the inkjet ink composition included in the ink treatment liquid set according to the present embodiment will be described.

[0123] 3. Inkjet ink composition

[0124] The inkjet ink composition included in the ink treatment liquid set according to the present embodiment is an aqueous pigment inkjet ink containing pigment particles and resin particles.

[0125] Pigment particles

[0126] Examples of the pigment particles include organic pigments of cyan, magenta, yellow, black, and the like, and special color pigments such as white pigments and bright pigments.

[0127] Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxane pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthraquinone pigments, indanthraquinone pigments, yellow anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, thioindigo pigments, isoindolinone pigments, azomethine pigments, dye chelates, dye lakes, nitro pigments, nitroso pigments, aniline black, and azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelated azo pigments.

[0128] Specific examples of organic pigments include the following pigments.

[0129] Examples of pigments used in cyan inks include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 16, 22, 60, etc.; CI Vat Blue 4, 60, etc., preferably one or a mixture of two or more selected from the group consisting of CI Pigment Blue 15:3, 15:4 and 60.

[0130] Examples of pigments used in magenta ink include CI Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 168, 184, 202, CI Pigment Violet 19, etc., preferably one or a mixture of two or more selected from the group consisting of CI Pigment Red 122, 202, 209 and CI Pigment Violet 19.

[0131] Examples of the pigment used in the yellow ink include CI Pigment Yellow 1, 2, 3, 12, 13, 14C, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 119, 110, 114, 128, 129, 138, 150, 151, 154, 155, 180, and 185. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Yellow 74, 109, 110, 128, and 138 is used.

[0132] The pigment used for the orange ink is CI Pigment Orange 36 or 43, or a mixture thereof.

[0133] The pigment used for the green ink is CI Pigment Green 7 or 36, or a mixture thereof.

[0134] Specific examples of carbon black include furnace black, lamp black, acetylene black, channel black, etc. (CI Pigment Black 7). Commercially available products include No. 2300, 900, MCF88, No. 20B, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B, etc. (trade names, manufactured by Mitsubishi Chemical Corporation); Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex35, U, V, 140U, Special Black 6, 5, 4A, 4, 250 (trade names, manufactured by Degussa Corporation); Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, 700, etc. (all of the above are trade names, manufactured by Columbia Carbon Company); Regal400R, 330R, 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, Elftex 12, etc. (trade names, manufactured by Cabot Corporation). These carbon blacks can be used alone or as a mixture of two or more.

[0135] As the bright pigment, there is no particular limitation as long as it is a pigment that can show brightness when attached to a medium, for example, metal particles of one or more alloys (also called metal pigments) selected from the group consisting of aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium and copper, and pearlescent pigments with pearl luster can be cited. As representative examples of pearlescent pigments, titanium dioxide-coated mica, fish scale foil, bismuth oxychloride and other pigments with pearl luster and interference luster can be cited. In addition, the bright pigment may also be subjected to a surface treatment for inhibiting reaction with water.

[0136] In addition, as white pigment, metal compounds such as metal oxides, barium sulfate, and calcium carbonate can be listed. As metal oxides, for example, titanium dioxide, zinc oxide, silicon dioxide, aluminum oxide, and magnesium oxide can be listed. In addition, white pigments can also use particles with a hollow structure.

[0137] The above-mentioned pigment particles may be used alone or in combination of two or more. From the viewpoint of storage stability such as light resistance, weather resistance, and gas resistance, the pigment particles are preferably organic pigments.

[0138] The pigment particles are preferably able to be stably dispersed in the ink. For example, the pigment particles can be modified by oxidizing or sulfonating the surface of the pigment particles using ozone, hypochlorous acid, fuming sulfuric acid, etc., thereby using them as self-dispersible pigment particles, or they can be dispersed using a resin dispersant.

[0139] Examples of the resin dispersant include polyvinyl alcohols, polyacrylic acid, acrylic acid-acrylonitrile copolymers, vinyl acetate-acrylate copolymers, acrylic acid-acrylate copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, styrene-α-methylstyrene-acrylic acid-acrylate copolymers, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, vinylnaphthalene-maleic acid copolymers, vinyl acetate-maleic acid copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers, and the like, and salts thereof.

[0140] Among them, copolymers of monomers having hydrophobic functional groups and monomers having hydrophilic functional groups, and polymers composed of monomers having both hydrophobic functional groups and hydrophilic functional groups are preferred. As the form of copolymer, any form of random copolymer, block copolymer, alternating copolymer, and graft copolymer can be used.

[0141] The resin dispersant described here has the function of improving the dispersibility of the pigment particles. The resin dispersant is, for example, water-soluble. And / or the resin dispersant is present around the pigment particles by attaching to the pigment or the like.

[0142] The content of the resin dispersant can be appropriately selected according to the pigment particles to be dispersed, but is preferably 5 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 120 parts by mass or less, relative to 100 parts by mass of the content of the pigment particles in the ink.

[0143] The content of the pigment particles in the ink is preferably 0.3% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, further preferably 1 to 10% by mass, and particularly preferably 1.5 to 5% by mass, relative to the total mass of the ink. If the content of the pigment particles is within the above range, it is difficult for the nozzle of the inkjet recording device to be clogged, and the color concentration can be fully satisfied. In addition, if the content of the pigment particles is above the above range, it is easier to form an image with excellent color development.

[0144] 3.2. Resin particles

[0145] As the resin particles, the same resin particles as those in the water-insoluble component that may be contained in the above-mentioned treatment liquid composition can be used.

[0146] 3.3. Physical properties of particle components

[0147] The volume average particle size of the above-mentioned particle components such as the pigment particles and the resin particles contained in the inkjet ink composition is 20 to 500 nm.

[0148] The volume-based average particle size (D50) (also referred to as "volume average particle size") of the particle component (before ink mixing) is 20 nm or more, preferably 50 nm or more, more preferably 80 nm or more, further preferably 110 nm or more, and particularly preferably 150 nm or more. In addition, the volume average particle size of the particle component is 500 nm or less, preferably 400 nm or less, more preferably 300 nm or less, further preferably 250 nm or less, and particularly preferably 200 nm or less. If the volume average particle size is within this range, it is easy to obtain and easy to make the characteristics become preferred characteristics. In addition, if the volume average particle size of the particle component is within the above range, the particle component is difficult to settle, which can make the dispersion stability good. In addition, there is a tendency that the nozzle clogging and the like are difficult to occur when applied to an inkjet recording device.

[0149] The volume average particle size of the particle component can be measured by a particle size distribution measuring device based on the laser diffraction scattering method. As a particle size distribution measuring device, for example, a particle size distribution meter based on the dynamic light scattering method (for example, "Microtrac UPA" manufactured by Nikkiso Co., Ltd.) can be cited.

[0150] The content of the particle component is 0.2% by mass or more and 40% by mass or less, preferably 2% by mass or more and 30% by mass or less, more preferably 4% by mass or more and 20% by mass or less, and further preferably 6% by mass or more and 15% by mass or less, in terms of solid content, relative to the total mass of the inkjet ink composition.

[0151] The above-mentioned pigment particles, resin particles and other particle components contained in the inkjet ink composition are preferably anionic. The above-mentioned treatment liquid composition contains a polyamide epihalohydrin polymer and a specific quaternary ammonium salt polymer as cationic polymers. Therefore, if the pigment particles, resin particles and other particle components of the ink are anionic, the treatment liquid composition and the ink will effectively undergo a coagulation reaction when mixed, and there is a tendency to obtain more excellent color development.

[0152] As the anionic pigment particles, preferably there are pigments having a dispersant having an anionic group on the surface. Examples of the dispersant having an anionic group include -COO- or -SO3 - Acts as a dispersant for anionic groups.

[0153] As the anionic resin particles, there can be mentioned resin particles having anionic functional groups such as carboxyl, sulfonic, and hydroxyl groups, and preferably anionic urethane resins. Among the commercially available products of the above-mentioned urethane resins, as anionic urethane resins, there can be mentioned Superflex 460, 460s, 840, etc. manufactured by Daiichi Kogyo Seiyaku Co., Ltd.; Takelac WS-5000, WS-6021, W-512-A-6, etc. manufactured by Mitsui Chemicals Polyurethane Co., Ltd.

[0154] 3.4. Water

[0155] The inkjet ink composition included in the ink treatment liquid set according to the present embodiment is a water-based pigment inkjet ink and contains water. "Water-based" means containing water as a main solvent. The water is the same as the water that can be contained in the treatment liquid composition described above.

[0156] The water content is not particularly limited, and may be, for example, 40% by mass or more, 50% by mass or more, or 60% by mass or more relative to the total mass of the inkjet ink composition. The upper limit of the water content in the inkjet ink composition may be 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0157] 3.5. Organic solvents

[0158] The inkjet ink composition included in the ink treatment liquid set according to the present embodiment may contain an organic solvent. As the organic solvent, a water-soluble organic solvent is preferred. Such a water-soluble organic solvent may be the same as the organic solvent that may be contained in the treatment liquid composition described above.

[0159] When a water-soluble organic solvent is contained, the content of the water-soluble organic solvent is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the total mass of the inkjet ink composition. In addition, the content of the water-soluble organic solvent is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more, relative to the total mass of the inkjet ink composition.

[0160] Surfactants

[0161] The inkjet ink composition included in the ink treatment liquid set according to the present embodiment may contain a surfactant. The surfactant may be the same as the surfactant that may be contained in the treatment liquid composition described above, and the content thereof may be the same.

[0162] 3.7. Other ingredients

[0163] The inkjet ink composition of the ink treatment liquid set according to the present embodiment may also contain wax, pH adjuster, preservative / mildewproof agent, rust inhibitor, chelating agent, viscosity modifier, solubilizer, antioxidant, etc. as needed. These components are the same as those that may be contained in the above-mentioned treatment liquid composition, and therefore, description thereof is omitted.

[0164] 3.8. Manufacturing method

[0165] The inkjet ink composition included in the ink treatment liquid set according to the present embodiment is obtained by mixing the above-mentioned components in an arbitrary order and removing impurities by filtering as needed. As a method for mixing the components, it is preferable to use a method in which the materials are sequentially added to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed. As a filtering method, centrifugal filtration, filter filtration, etc. can be performed as needed.

[0166] 3.9. Physical Properties of Inkjet Ink Compositions

[0167] As the physical properties of the inkjet ink composition included in the ink treatment liquid set according to the present embodiment, pH, surface tension, viscosity, etc. can be adjusted to a desired range.

[0168] The pH of the inkjet ink composition exceeds 8. Preferably, the pH exceeds 9, more preferably, the pH exceeds 10, and further preferably, the pH exceeds 11. When the pH of the inkjet ink composition is within the above range, the ink is easily converted into an unstable dispersion state when mixed with the treatment liquid composition, and aggregation of particle components is promoted, and the color development property tends to be further improved.

[0169] The physical properties such as surface tension and viscosity may be the same as those of the above-mentioned treatment liquid composition.

[0170] 4. Treatment methods

[0171] A processing method according to one embodiment of the present invention comprises:

[0172] an attachment step of attaching the above-mentioned treatment liquid composition to the fabric; and

[0173] a heating step of heating the fabric to which the treatment liquid composition is attached,

[0174] The surface temperature of the fabric in the heating step is 100° C. or higher.

[0175] The treatment method involved in this embodiment performs the following treatment: the treatment includes a step of heating the cloth to which the above-mentioned treatment liquid composition is attached so that the surface temperature of the cloth is above 100°C. By implementing this treatment method, it is possible to achieve both excellent color development and excellent wet friction fastness.

[0176] Hereinafter, each step of the processing method according to the present embodiment will be described.

[0177] 4.1. Attachment process

[0178] The treatment method according to the present embodiment includes a step of attaching the above-mentioned treatment liquid composition to the fabric. The treatment liquid composition and the fabric are as described above, and therefore, description thereof will be omitted.

[0179] As a method for attaching the treatment liquid composition to the fabric (coating method), for example, a method of immersing the fabric in the treatment liquid composition (immersion coating), a method of applying the treatment liquid composition using a roller coater, etc. (roller coating), a method of spraying the treatment liquid composition by a spray device, etc. (spraying), a method of spraying the treatment liquid composition by an inkjet method (inkjet coating), etc., any method can be used. If the treatment liquid composition is applied by inkjet coating, it is easy to control the treatment liquid composition to be uniformly attached to the fabric, which is preferred. In addition, if the treatment liquid composition is applied by immersion coating or spraying, it is possible to apply the treatment liquid composition to the fabric in a short time, which is preferred.

[0180] The coating amount of the treatment liquid composition is preferably 50 to 200 g / m2 per unit area of ​​the fabric. 2 , more preferably 70 to 170 g / m 2 , more preferably 90 to 140 g / m 2 , particularly preferably 100 to 120 g / m 2 When the coating amount of the treatment liquid composition is within the above range, the effects of the present invention may be more easily achieved.

[0181] 4.2. Heating process

[0182] The treatment method according to the present embodiment includes a heating step of heating the fabric to which the treatment liquid composition is attached after the above-mentioned attachment step. The heating method is not particularly limited, and examples thereof include convection heat drying, radiation heat drying, and conduction heat drying. In addition, as a heat source used for heating, heat generated by a combustible gas burner, a carbon heater / ceramic heater / halogen lamp, or an infrared lamp can be used.

[0183] The lower limit of the surface temperature of the fabric in the heating process is preferably 40°C or more, more preferably 80°C or more, and further preferably 100°C or more. In addition, the upper limit of the surface temperature of the fabric in the heating process is preferably 180°C or less. By setting the heating temperature to 180°C or less, damage caused by thermal stress on the fabric during heating and drying can be suppressed. In addition, by setting the heating temperature to a value above the lower limit, the moisture, solvent, etc. contained in the treatment liquid composition can be efficiently evaporated to promote the drying of the treated fabric. In addition, when cotton is contained in the raw materials constituting the fabric, by setting the heating temperature to 100°C or more, the cross-linking reaction between the polyamide epihalohydrin polymer contained in the treatment liquid composition and the cellulose fibers in the cotton fabric can be promoted.

[0184] According to this treatment liquid composition, by using it for pretreatment of a recording medium when recording an image using the inkjet ink composition, an image having excellent at least wet friction fastness, color development property and light fastness can be obtained.

[0185] 5. Examples and Comparative Examples

[0186] The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" below is based on mass.

[0187] 5.1. Preparation of treatment liquid composition

[0188] The components were mixed in the amounts shown in Tables 1 to 4 below, stirred at room temperature for 2 hours, and then filtered using a membrane filter with a pore size of 5 μm to obtain each treatment liquid composition. In addition, the units of the contents of the compositions shown in Tables 1 to 4 below are mass %.

[0189] 5.2. Preparation of inkjet ink composition

[0190] The components are mixed in the amounts shown in the following black ink composition example, stirred at room temperature for 2 hours, and then filtered using a membrane filter with a pore size of 5 μm to obtain an inkjet ink composition (black ink). In addition, in the following black ink composition example, the content of the pigment is the pigment solid content, and the content of the resin emulsion is the resin solid content. In addition, the carbon black pigment used to prepare the inkjet ink composition uses the following substance: the carbon black pigment and the pigment dispersant (not described in the following composition example) which is a water-soluble styrene acrylic resin are mixed in water in a mass ratio of 1:1 (pigment: pigment dispersant), and then fully stirred to obtain a black pigment dispersion.

[0191] Composition example of black ink

[0192]

[0193] The above-mentioned black ink will be supplemented with explanation.

[0194] Carbon black pigment: CI Pigment Black 7

[0195] WS6021: Takelac WS-6021, a trade name manufactured by Mitsui Chemicals, Inc., solid content: 30% by mass, urethane resin

[0196] EDTA: Ethylenediaminetetraacetic acid, metal chelating agent

[0197] Olfine E1010: a trade name manufactured by Nissin Chemical Industry Co., Ltd., an acetylene glycol-based surfactant, HLB = 14

[0198] Surfynol 104: a trade name produced by Nissin Chemical Industry Co., Ltd., an acetylene glycol-based surfactant, HLB = 4

[0199] The pH of the black ink is more than 8. The pH was measured by using a benchtop pH meter Model F-72 (manufactured by Horiba, Ltd.) and immersing an electrode portion in the inkjet ink composition.

[0200] 5.3 Recording Media

[0201] As the recording medium, the following fabrics were used.

[0202] Cotton cloth

[0203] Fiber: Cotton

[0204] Type: Taffeta

[0205] Composition: Cotton 100%

[0206] Weight: 8.04~8.55(g / m 2 )

[0207] Specifications: 145~150(cm)

[0208] Manufacturing company: A.FERRARIO

[0209] Whiteness L* value: 91.5

[0210] In addition, the L* value of the fabric was measured using a colorimeter "Gretag Macbeth Spectrolino" (product name, manufactured by X-Rite Corporation).

[0211]

[0212]

[0213]

[0214]

[0215] Supplementary explanations are given for the records in Tables 1 and 2 above.

[0216] Composition

[0217] The following are the additional information on polyamide epihalohydrin polymers, quaternary ammonium salt polymers, resin particles, surfactants and preservatives:

[0218] Water resistant agent

[0219] Polyamide epihalohydrin polymer

[0220] Polyamide-epichlorohydrin polymer: "WS4020", manufactured by Starlight PMC

[0221] Polyamide polyamine-epichlorohydrin polymer: "AF-255", manufactured by Arakawa Chemical Industries, Ltd.

[0222] ·Dimethylamine-ethylenediamine-epichlorohydrin polycondensate: "PE-30", manufactured by Yokkaichi Synthetic Co., Ltd.

[0223] MEKO Blocked Isocyanate

[0224] ·Methyl ethyl ketone oxime: manufactured by HUNTSMAN, PHOBOL_XAN

[0225] DMP blocked isocyanate

[0226] ·Dimethylpyrazole blocked isocyanate: Fixer #200, manufactured by Murayama Chemical Laboratories, Ltd.

[0227] ·Dimethylpyrazole blocked isocyanate: NK ASSIST NY-30, manufactured by Nikka Chemical Co., Ltd.

[0228] Cationic polymers

[0229] Quaternary ammonium salt polymer B: "PAS-J-81", manufactured by NITTBO MEDICAL, diallyldimethylammonium chloride-acrylamide copolymer, average molecular weight 180,000

[0230] Modified polyamine compound: "DK6810", manufactured by Seikyo PMC Co., Ltd.

[0231] ·Polyamine compound: "Jetfix N700", manufactured by Satoda Chemical Co., Ltd.

[0232] ·Polyamine compound: "Jetfix220", manufactured by Satoda Chemical Co., Ltd.

[0233] Surfactants

[0234] Acetylene glycol: trade name "Surfynol 485", manufactured by Nissin Chemical Industry Co., Ltd., HLB = 17

[0235] preservative

[0236] Proxel XL2: a trade name manufactured by Lonza

[0237] Processing conditions

[0238] The drying temperature after application of the pretreatment liquid composition (treatment liquid composition) and the drying temperature after printing with ink are shown in the table, as well as the surface temperature of the fabric when subjected to heat drying treatment using a conveyor drying oven "Economax D" (trade name of M&R Co.).

[0239] Evaluation Project

[0240] The spray stability evaluation test was conducted using the "1008 + This is done by combining a "spray controller" with a two-fluid nozzle that produces a flat spray pattern.

[0241] The pH was measured by using a tabletop pH meter Model F-72 (manufactured by Horiba, Ltd.) and immersing the electrode portion in the treatment liquid composition.

[0242] Evaluation methods

[0243] As evaluation tests, spray stability, color development, friction fastness, texture, and light resistance were evaluated. The evaluation method is as follows.

[0244] 5.4.1. Spraying stability (two-fluid nozzle)

[0245] The 1008 + The composition of each treatment liquid obtained above was adjusted to 110 g / m per unit area by combining a spray controller and a two-fluid nozzle that generates a flat spray pattern. 2 After applying a coating amount of 100%, the coating was evenly applied on the surface of the fabric described in the above "4.3. Recording medium". At this time, the coating weight change consumed during the coating treatment time of the treatment liquid composition was monitored, and the ability to apply a prescribed amount of coating without nozzle clogging was evaluated as the spraying stability. The spraying stability was determined as follows:

[0246] Judgment Criteria

[0247] A: The coating weight change rate at the end of coating is less than ±10% relative to the initial setting value.

[0248] B: The coating weight change rate at the end of coating is ±10% or more and less than 20% relative to the initial setting value.

[0249] C: The coating weight change rate at the end of coating is ±20% or more relative to the initial setting value.

[0250] 5.4.2. Color rendering (black ink_100% Duty)

[0251] The fabric coated with the treatment liquid composition by the above method was subjected to a heating and drying treatment for 7 minutes at the drying temperature described in the table using a conveyor belt drying oven "Economax D" (manufactured by M&R Co., Ltd.), thereby completing the treatment of the fabric. The inkjet ink composition prepared as described above was attached to the fabric by an inkjet method using an inkjet printer (product name "PX-G930", manufactured by Seiko Epson Corporation) to print an image. The printing pattern (image) was set to a resolution of 1440×720 dpi, the printing range was set to 210 mm×297 mm, and a full-page image was printed.

[0252] Here, the term “solid image” refers to an image in which dots are recorded on all pixels that are pixels of the minimum recording unit area defined by the recording resolution.

[0253] The cloth with the inkjet ink composition attached was subjected to a heat drying treatment at 160°C for 5 minutes using a conveyor drying oven "EconomaxD" (manufactured by M&R), and the temperature was restored to 25°C to obtain a printed product. The optical density (hereinafter also referred to as "OD value") of the printed cloth was measured using a fluorescence spectrophotometer ("FD-7", manufactured by Konica Minolta) to evaluate the color development. The judgment was made as follows:

[0254] Judgment Criteria

[0255] AA: OD value is 1.5 or more. (Particularly good)

[0256] A: OD value is 1.4 or more and less than 1.5. (Good)

[0257] B: OD value is 1.25 or more and less than 1.4.

[0258] D: OD value is less than 1.25.

[0259] 5.4.3. Friction fastness (discoloration)

[0260] For the fabric printed with 100% duty by the above method, the dry and wet abrasion resistance were tested using the test method based on ISO105-X12 and judged according to the following criteria. The wet and dry abrasion resistance were judged according to the following criteria as the difference in OD value caused by discoloration before and after the abrasion resistance test.

[0261] Determination criteria of dry friction strength

[0262] AA: The difference in OD value before and after the abrasion resistance test is less than 0.15. (Extremely good)

[0263] A: The difference in OD value before and after the abrasion resistance test is less than 0.15 or more and less than 0.20. (Good)

[0264] B: The difference in OD value before and after the abrasion resistance test is 0.20 or more and less than 0.25.

[0265] C: The difference in OD value before and after the abrasion resistance test is 0.25 or more.

[0266] Determination criteria of wet friction strength

[0267] AA: The difference in OD value before and after the abrasion resistance test is less than 0.20. (Extremely good)

[0268] A: The OD value difference before and after the abrasion resistance test is 0.20 or more and less than 0.25. (Good)

[0269] B: The difference in OD value before and after the abrasion resistance test is 0.25 or more and less than 0.30.

[0270] D: The difference in OD value before and after the abrasion resistance test is 0.30 or more.

[0271] 5.4.4. Texture (shear stiffness)

[0272] The shear stiffness of the fabric printed with 100% duty by the above method was evaluated using a tensile shear tester: KES-FBI-A manufactured by Katotech Co., Ltd. The texture was judged according to the following criteria using the shear stiffness value.

[0273] Judgment Criteria

[0274] AA: Shear rigidity is less than 6.0 gf / cm·deg.

[0275] A: Shear rigidity is 6.0 gf / cm·deg or more and less than 8.0 gf / cm·deg.

[0276] B: Shear rigidity is 8.0 gf / cm·deg or more and less than 10.0 gf / cm·deg.

[0277] D: Shear rigidity is 10.0 gf / cm·deg or more.

[0278] 5.4.5. Lightfastness (yellowing)

[0279] The fabric coated with the treatment liquid composition under the conditions described in "4.4.2. Color Development (Black Ink_100% Duty)" and dried was irradiated with 20 MJ / m using a xenon lamp weathering tester (XL75s) manufactured by Suga Test Instruments Co., Ltd. 2 The xenon light with a cumulative irradiance of . For the pretreated fabric before and after the irradiation, the degree of discoloration of the fabric was derived as a color difference ΔEab using a fluorescence spectrophotometer ("FD-7", manufactured by Konica Minolta). In addition, the fabric used for evaluation was white cotton described in the above "4.3 Recording Medium", and the L* value was 91.5. The light resistance was determined using the color difference value according to the following criteria.

[0280] Judgment Criteria

[0281] A: The color difference is less than 2.0.

[0282] B: The color difference is 2.0 or more and less than 4.0.

[0283] D: The color difference is 4.0 or more.

[0284] 5.5 Evaluation results

[0285] The evaluation results are shown in Tables 1 to 4 described above.

[0286] As can be seen from the comparison between the examples and the comparative examples, the treatment liquid composition, the inkjet ink composition and the treatment liquid composition, and the recording method according to the present embodiment can achieve both excellent color development and excellent wet friction fastness.

[0287] In more detail, according to the processing liquid composition of the embodiment, an image with good wet friction fastness and color development can be obtained through the effect of improving wet friction fastness and / or water resistance brought by the water-resistant agent and the effect of combining color development and fastness brought by the coagulant.

[0288] In the above treatment liquid composition,

[0289] Can be applied to fabric for use.

[0290] In the above treatment liquid composition,

[0291] The L* value of the fabric may be 90 or more.

[0292] According to this treatment liquid composition, even for a cloth which is prone to noticeable yellowing, a recorded object with suppressed yellowing can be obtained.

[0293] In the above treatment liquid composition,

[0294] The pH of the treatment fluid composition may be less than 7.

[0295] According to the treatment liquid composition, the reactivity with the inkjet ink composition becomes better, and when the inkjet ink composition and the treatment liquid composition come into contact, the dispersion destabilization and aggregation of the components in the ink are more easily promoted, and an image with better friction fastness and / or color development can be formed.

[0296] The ink set is a set of an inkjet ink composition and any of the above-mentioned treatment liquid compositions,

[0297] The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles. The ink composition has a pH of more than 8 and contains particle components having a volume average particle diameter of 20 nm to 500 nm.

[0298] According to this ink set, since the above-mentioned treatment liquid composition is used, an image having both excellent color development and excellent wet friction fastness can be obtained.

[0299] In the above ink set,

[0300] The particle component may be anionic.

[0301] According to this ink set, since the particle components such as pigment particles and resin particles in the inkjet ink composition are anionic, when the processing liquid composition and the ink are mixed, the water-resistance agent in the processing liquid composition further efficiently produces a coagulation reaction, and an image with better color development can be obtained.

[0302] The processing methods include:

[0303] an attachment step of attaching any of the above-mentioned treatment liquid compositions to the fabric; and

[0304] a heating step of heating the fabric to which the treatment liquid composition is attached,

[0305] The surface temperature of the fabric in the heating step is 100° C. or higher.

[0306] According to this treatment method, the water, solvent, etc. contained in the treatment liquid composition can be evaporated efficiently to dry the treated fabric. In addition, when the raw material constituting the fabric includes cotton, by setting the heating temperature to 100° C. or higher, the crosslinking reaction between the water-resistant agent contained in the treatment liquid composition and the cellulose fibers in the cotton fabric can be promoted.

[0307] The above-mentioned embodiments and modifications are merely examples and are not limiting. For example, the embodiments and modifications may be appropriately combined.

[0308] The present invention includes a configuration substantially the same as the configuration described in the embodiment, such as a configuration with the same function, method and result or a configuration with the same purpose and effect. In addition, the present invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that can play the same role and effect as the configuration described in the embodiment or a configuration that can achieve the same purpose. In addition, the present invention includes a configuration in which a known technology is added to the configuration described in the embodiment.

[0309] The following contents are derived from the above-mentioned embodiments and modifications.

[0310] The treatment fluid composition contains:

[0311] A water-resistance agent selected from polyamide epihalohydrin polymers and dimethylpyrazole blocked isocyanates; and

[0312] Polyamine compounds.

[0313] According to this treatment liquid composition, by using it for pretreatment of a recording medium when recording an image using the inkjet ink composition, an image having excellent at least wet friction fastness, color development property and light fastness can be obtained.

[0314] More specifically, according to the treatment liquid composition, an image with good wet friction fastness and color development can be obtained by the effect of improving wet friction fastness and / or water resistance brought by the water-resistant agent and the effect of achieving both color development and fastness brought by the coagulant.

[0315] In the above treatment liquid composition,

[0316] Can be applied to fabric for use.

[0317] In the above treatment liquid composition,

[0318] The L* value of the fabric may be 90 or more.

[0319] According to this treatment liquid composition, even for a cloth which is prone to noticeable yellowing, a recorded object with suppressed yellowing can be obtained.

[0320] In the above treatment liquid composition,

[0321] The pH of the treatment fluid composition may be less than 7.

[0322] According to the treatment liquid composition, the reactivity with the inkjet ink composition becomes better, and when the inkjet ink composition and the treatment liquid composition come into contact, the dispersion destabilization and aggregation of the components in the ink are more easily promoted, and an image with better friction fastness and / or color development can be formed.

[0323] The ink set is a set of an inkjet ink composition and any of the above-mentioned treatment liquid compositions,

[0324] The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles. The ink composition has a pH of more than 8 and contains particle components having a volume average particle diameter of 20 nm to 500 nm.

[0325] According to this ink set, since the above-mentioned treatment liquid composition is used, an image having both excellent color development properties and excellent wet friction fastness can be obtained.

[0326] In the above ink set,

[0327] The particle component may be anionic.

[0328] According to this ink set, since the particle components such as pigment particles and resin particles in the inkjet ink composition are anionic, when the processing liquid composition and the ink are mixed, the water-resistance agent in the processing liquid composition further efficiently produces a coagulation reaction, and an image with better color development can be obtained.

[0329] The processing methods include:

[0330] an attachment step of attaching any of the above-mentioned treatment liquid compositions to the fabric; and

[0331] a heating step of heating the fabric to which the treatment liquid composition is attached,

[0332] The surface temperature of the fabric in the heating step is 100° C. or higher.

[0333] According to this treatment method, the water, solvent, etc. contained in the treatment liquid composition can be evaporated efficiently to dry the treated fabric. In addition, when the raw material constituting the fabric includes cotton, by setting the heating temperature to 100° C. or higher, the crosslinking reaction between the water-resistant agent contained in the treatment liquid composition and the cellulose fibers in the cotton fabric can be promoted.

Claims

1. A treatment liquid composition, It is characterized in that The treatment liquid composition comprises: A water-resistance agent selected from polyamide epihalohydrin polymers and dimethylpyrazole blocked isocyanates; and Polyamine compounds, The content of the polyamide epihalohydrin polymer is 0.10 mass % or more and 5.0 mass % or less relative to the total amount of the treatment liquid composition, The content of the dimethylpyrazole blocked isocyanate is 0.1 mass % or more and 15.0 mass % or less relative to the total amount of the treatment liquid composition, The content of the polyamine compound is 0.2 mass % or more and 10.0 mass % or less relative to the total amount of the treatment liquid composition.

2. The treatment liquid composition according to claim 1, It is characterized in that The treatment liquid composition is applied to fabric for use.

3. The treatment liquid composition according to claim 2, It is characterized in that The L* value of the fabric is 90 or more.

4. The treatment liquid composition according to any one of claims 1 to 3, It is characterized in that The pH of the treatment fluid composition is less than 7.

5. A combination of an inkjet ink composition and a treatment liquid composition, It is characterized in that The set is a set of an inkjet ink composition and a treatment liquid composition according to any one of claims 1 to 4, The inkjet ink composition is a water-based pigment inkjet ink containing pigment particles and resin particles. The ink composition has a pH of more than 8 and contains particle components having a volume average particle diameter of 20 nm to 500 nm.

6. The combination of the inkjet ink composition and the treatment liquid composition according to claim 5, It is characterized in that The particle component is anionic.

7. A method of treatment, It is characterized in that The processing method has the following features: an attachment step of attaching the treatment liquid composition according to any one of claims 1 to 4 to a fabric; and a heating step of heating the fabric to which the treatment liquid composition is attached, The surface temperature of the fabric in the heating step is 100° C. or higher.

Images